Five-Coordinate Complex [RuHCl(CO)(PPri₃)₂] as a Precursor for the Preparation of New Cyclopentadienylruthenium Compounds Containing Unsaturated η1-Carbon Ligands

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Abstract

The five-coordinate complex [RuHCl(CO)(PPri3)2] (1) reacts with cyclopentadiene in methanol under reflux to give [RuH(η5-C5H5)(CO)(PPri3)] (2) and [HPPri3]Cl. The protonation of 2 in dichloromethane-d2 leads to the dihydrogen complex [Ru(η5-C5H5)(η2-H2)(CO)(PPri3)]BF4 (3) in equilibrium with traces of the dihydrido tautomer [RuH2(η5-C5H5)(CO)(PPri3)]BF4 (4). The reaction of 2 with HBF4·Et2O in acetone affords the solvated complex [Ru(η5-C5H5)(CO){η1-OC(CH3)2}(PPri3)]BF4 (5), which reacts with CO, dimethyl acetylenedicarboxylate, and NaCl to give [Ru(η5-C5H5)(CO)2(PPri3)]BF4 (6), [Ru(η5-C5H5){η2-C2(CO2CH3)2}(CO)(PPri3)]BF4 (7), and [Ru(η5-C5H5)Cl(CO)(PPri3)] (8), respectively. Complex 5 also reacts with alkyn-1-ols. The reaction with 1,1-diphenyl-2-propyn-1-ol leads to the allenylidene complex [Ru(η5-C5H5)(CCCPh2)(CO)(PPri3)]BF4 (9), which affords [Ru(η5-C5H5){C(OH)CHCPh2}(CO)(PPri3)]BF4 (10) by reaction with water. 10 is converted into the acyl derivative [Ru(η5-C5H5){C(O)CHCPh2}(CO)(PPri3)] (11), when a CH2Cl2 solution of 10 is passed through an Al2O3 column. The structure of 11 was determined by an X-ray investigation. The reaction of 5 with 2-propyn-1-ol leads to the α,β-unsaturated hydroxycarbene complex [Ru(η5-C5H5){C(OH)CHCH2}(CO)(PPri3)]BF4 (12). Similarly to 10, 12 is converted into [Ru(η5-C5H5){C(O)CHCH2}(CO)(PPri3)] (13), when the solutions of 12 are passed through an Al2O3 column. Treatment of 5 with 1-ethynyl-1-cyclohexanol leads to a mixture of organometallic compounds including [Ru(η5-C5H5){C(OH)CHC(CH2)4CH2}(CO)(PPri3)]BF4 (14). Chromatography of the mixture affords [Ru(η5-C5H5){C(O)CHC(CH2)4CH2}(CO)(PPri3)] (15) and [Ru(η5-C5H5){C⋮CCCH(CH2)3CH2}(CO)(PPri3)] (16). 9 reacts with alcohols and thiols to give [Ru(η5-C5H5){C(ER)CHCPh2}(CO)(PPri3)]BF4 (ER = OMe (17), OEt (18), SPrn (21)), which by treatment with NaOMe afford [Ru(η5-C5H5){C(ER)CCPh2}(CO)(PPri3)] (ER = OMe (19), OEt (20), SPrn (22)). Similarly, the reaction of 9 with benzophenone imine leads to [Ru(η5-C5H5){C(CHCPh2)NCPh2}(CO)(PPri3)]BF4 (23), which by reaction with NaOMe gives [Ru(η5-C5H5){C(NCPh2)CCPh2}(CO)(PPri3)] (24). The structure of 23 was also determined by an X-ray investigation. The CN bond lengths are 1.283(9) and 1.252(9) Å, while the C−N−C angle is 149.9(6)°.

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